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The format is a list of pairs, where the first item is the scriptSig required to spend and the second is the scriptPubKey. The third item is ignored (useful for comments).
script_valid.json contains only valid scriptSig/scriptPubKey pairs.
script_invalid.json contains only invalid scriptSig/scriptPubKey pairs.
valid/invalid are defined by the rules of transaction validation, and the unit test actually constructs transactions and runs the verification routine on them to make sure that they succeed or fail, as expected.